The Masters Battle is a match type in Pokémon Battle Revolution held in Stargazer Colosseum, after the player wins the Pokétopia Championship. The Masters Battle consists of eight sets of four trainers, with a Colosseum Master heading each set. All the trainers in the Masters Battle use highly advanced combinations and tactics, and may need a specific approach to defeat. Initially, only Set 1 will be unlocked. The trainer must beat each Set to unlock the next Set and can rechallange any unlocked Set at anytime. On a side note, Mysterial's team, who appear heading Sets 4 and 8, changes depending on whether the player used Pokémon Diamond or Pokémon Pearl in transferring their Pokémon to Pokémon Battle Revolution.

Intelligence in a CPU trainer has never before been seen on a level such as this. All battles may need to be approached from a different angle in order to win. Above all, none of the Masters Battle trainers are to be taken lightly.

The list below contains all known Pokémon, moves, items and abilities used by each trainer in Masters Battle - Sets 1 though 4.